Abstract

For decades the optimization of polycrystalline absorbers has been done using an Edisonian approach, where trial and error and complex design of experiments in large parameter spaces have driven efficiencies to the record values we see today – CIGS at 22.5%, 22.1% for CdTe, 21.3% for high purity multi-crystalline silicon. Appropriate growth parameters are critical to ensure good quality crystals with low concentration of structural defects - low dislocation density and large grain sizes. However, to bridge the gap between the efficiencies today and the fundamental Shockley-Queisser limit for these materials a much more fundamental understanding of the role and interaction between composition, structure, defect density and electrical properties is required. In recent years multiple novel characterization techniques have shown the potential that nanoscale characterization can have in deciphering the composition of grain boundaries in materials like CIGS and CdTe. However, high resolution has come at the cost of small sampling areas and number of specimens, making it extremely difficult to draw conclusions based on the characteristic small sampling sizes. The missing links thus far have been: (1) the lack of statistical meaningfulness of the nanosclae studies and (2) the direct correlation of compositional variations to electrical performance with nanoscalemore » resolution. In this work we present the use of synchrotron-based nano-X-ray fluorescence microscopy (nano-XRF), x-ray absorption nanospectroscopy (nano-XAS) coupled with nano-x-ray beam induced current (nano-XBIC) as ideal tools for investigating elemental, chemical and electrical properties of large areas of solar cell materials at the sub-micron scale with very high sensitivity. We show how the technique can provide statistical valuable information regarding the elemental segregation in CIGS and the direct correlation to current collection. For example, we demonstrate that Cu and Ga (and with that, CGI and GGI) correlate positively, and In negatively with charge collection efficiency for cells with low Ga content, both at grain boundaries and in grain cores. For cells with high Ga content, the charge collection efficiency depends to much lesser extent on the elemental distribution. The objective is three folded: (1) develop an x-ray in-situ microscopy capability to simulate growth and processing conditions, (2) apply it to elucidate performance-governing defect kinetics in chalcogenide solar cell materials, and (3) to study approaches to engineer materials from the nanoscale up. The development of these capabilities will enable experimental characterization to take place under actual processing and operating conditions and it will have impact well beyond the proposed research, enabling future studies on a large variety of materials system where electronic properties depend on underlying structural or chemical inhomogeneities.« less

@article{osti_1398242,
title = {In-situ X-ray Nanocharacterization of Defect Kinetics in Chalcogenide Solar Cell Materials},
author = {Bertoni, Mariana and Lai, Barry and Masser, Jorg and Buonassisi, Tonio},
abstractNote = {For decades the optimization of polycrystalline absorbers has been done using an Edisonian approach, where trial and error and complex design of experiments in large parameter spaces have driven efficiencies to the record values we see today – CIGS at 22.5%, 22.1% for CdTe, 21.3% for high purity multi-crystalline silicon. Appropriate growth parameters are critical to ensure good quality crystals with low concentration of structural defects - low dislocation density and large grain sizes. However, to bridge the gap between the efficiencies today and the fundamental Shockley-Queisser limit for these materials a much more fundamental understanding of the role and interaction between composition, structure, defect density and electrical properties is required. In recent years multiple novel characterization techniques have shown the potential that nanoscale characterization can have in deciphering the composition of grain boundaries in materials like CIGS and CdTe. However, high resolution has come at the cost of small sampling areas and number of specimens, making it extremely difficult to draw conclusions based on the characteristic small sampling sizes. The missing links thus far have been: (1) the lack of statistical meaningfulness of the nanosclae studies and (2) the direct correlation of compositional variations to electrical performance with nanoscale resolution. In this work we present the use of synchrotron-based nano-X-ray fluorescence microscopy (nano-XRF), x-ray absorption nanospectroscopy (nano-XAS) coupled with nano-x-ray beam induced current (nano-XBIC) as ideal tools for investigating elemental, chemical and electrical properties of large areas of solar cell materials at the sub-micron scale with very high sensitivity. We show how the technique can provide statistical valuable information regarding the elemental segregation in CIGS and the direct correlation to current collection. For example, we demonstrate that Cu and Ga (and with that, CGI and GGI) correlate positively, and In negatively with charge collection efficiency for cells with low Ga content, both at grain boundaries and in grain cores. For cells with high Ga content, the charge collection efficiency depends to much lesser extent on the elemental distribution. The objective is three folded: (1) develop an x-ray in-situ microscopy capability to simulate growth and processing conditions, (2) apply it to elucidate performance-governing defect kinetics in chalcogenide solar cell materials, and (3) to study approaches to engineer materials from the nanoscale up. The development of these capabilities will enable experimental characterization to take place under actual processing and operating conditions and it will have impact well beyond the proposed research, enabling future studies on a large variety of materials system where electronic properties depend on underlying structural or chemical inhomogeneities.},
doi = {10.2172/1398242},
journal = {},
number = ,
volume = ,
place = {United States},
year = 2016,
month = 9
}

The work reported was directed towards evaluation of new amorphous compounds for application in solar cells. The ternary A/sup II/B/sup IV/C/sub 2//sup V/ chalcopyrite systems were selected because of their inexpensive constituent elements and tetrahedral geometry. Polycrystalline samples of the ternary arsenides with Cd and Zn as the group II element and Ge, Si, Sn as the group IV element were synthesized. Thin films were deposited by vacuum evaporation of the bulk ternary arsenides. The stoichiometries of the films were irreproducible and were usually deficient in the lower vapor pressure group IV element. Films made by evaporating polycrystalline ZnAs/sub 2/,more » which also has a tetrahedral bonding structure, had stoichiometries generally in the range from Zn/sub 3/As/sub 2/ to ZnAs/sub 2/. The former compound is formed by the decomposition of ZnAs/sub 2/ to Zn/sub 3/As/sub 2/ and As/sub 4/. The intermediate stoichiometries are thought to be mixtures of the decomposition products. Preliminary results from annealing of the films indicate that heat treatment produces the stoichiometries expected for one of the two forms of zinc arsenide. The as-deposited films are amorphous when the substrate temperature is kept below 100/sup 0/C. The a-ZnAs/sub x/ films were characterized. EDAX and Auger analysis showed that films were homogeneous in the plane of the substrate, but that some variation occurred in the depth profile of the films. This change in composition is consistent with the sample decomposition which occurs during the evaporation. The as-prepared films were p-type with room temperature resistivities on the order of 10/sup 2/-10/sup 4/..cap omega..-cm. Optical absorption measurements gave optical band gap values of 1.2 eV for a-Zn/sub 3/As/sub 2/ and 1.5 eV for a-ZnAs/sub 2/. The ZnAs/sub x/ films were photoconductive.« less

Work performed on the project to synthesize A/sup II/B/sup IV/C/sub 2//sup V/ glasses and evaluate their potential use as solar cell materials is described. The major effort was directed towards preparation of these films by thermal evaporation of compounds synthesized during the first quarter. Films were produced from CdAs/sub 2/, CdSnAs/sub 2/, CdSiAs/sub 2/, ZnSiAs/sub 2/ and ZnAs/sub 2/. Only films from the last compound had a stoichiometry comparable to the starting material. The ternary films were deficient in the group IV element and films produced from CdAs/sub 2/ indicated the sample had undergone extensive decomposition. In addition to havingmore » good stoichiometries, the x-ray analysis of the ZnAs/sub 2/ films indicated they were amorphous. The work thus represents the first reported results of preparation of amorphous films of ZnAs/sub 2/. The optical and electrical properties of this material will be characterized in the next quarter.« less

This work describes the work performed during the first quarter of a new project to synthesize A/sup II/B/sup IV/C/sub 2//sup V/ glasses and evaluate their potential use as solar cell materials. The results of an extensive literature search on the ternary glasses showed that those composed of Zn and Cd as the group two element, Sn, Ge, Si as the group four, and As and P as the group five element comprise the most promising materials on the basis of cost, band gap, and tendency for glass formation. The initial analysis of the defect structure expected in the ternary glassesmore » showed that both radical and ionic defects are possible. The sparse results published in the literature indicate, however, that the former type is not important. The laboratory work was directed towards preparing bulk quantities of the ternary compounds. All the ternary arsenides have been prepared. 35 references.« less